EA029225B1 - Pour-point depressant - Google Patents

Abstract

The invention is related to production of additives for petroleum industry and can be used for lowering the pour point, dynamic viscosity, and as a means for preventing formation of asphaltene-resin-paraffin deposits during oil transportation and storage. The objective of the invention is provision of a new, efficient pour-point depressant for lowering the pour point and viscosity properties of highly paraffinic oils during transportation and storage, and broadening the raw materials base and the range of pour-point depressants on the basis of products of various hydrocarbon raw materials. The objective of the invention is attained by that a pour-point depressant consisting of a non-ionogenic surfactant - Laprol 5003-2B-10 or Laprol 6003-2B-18 - and a solvent includes additionally Flexoil CW 288 reagent and, as a non-ionogenic surfactant, includes additionally Laprol 3603-2-12, and includes stable gas condensate and light gasoil as a solvent, at the following proportion of the components, wt.%: F1exoil CW 288 reagent - 20-25; light gasoil - 15-25; Laprol 3603-2-12 or Laprol 5003-2B-10 or Laprol 6003-2B-18 - 2-5; stable gas condensate - the balance.

Description

The invention relates to the production of additives for the oil industry and can be used to reduce the pour point, dynamic viscosity, and also as a means of preventing the formation of asphaltoresin-paraffin deposits during transportation and storage of oil. The objective of the invention is to create a new effective depressant to reduce the freezing temperature and viscosity properties, high paraffin oils during production, transport and storage of oil, as well as the expansion of the resource base and the range of depressants based on products of various hydrocarbons. The task in the invention is solved by the fact that a depressant additive consisting of a non-ionic surfactant - Laprol 5003-2B-10 or Laprol 6003-2B-18 and a solvent, additionally contains the Reactor CA 288 and, as a non-ionic surfactant, also Laprol 3603 -2-12, and as a solvent, stable gas condensate and light gas oil in the following ratio of components, wt.%: Reagent Р1хоП СА 288 20-25; light gas oil 15-25; Laprol 3603-2-12 or Laprol 5003-2B-10 or Laprol 6003-2B-18 2-5; stable gas condensate - the rest.

029225

The invention relates to the production of additives for the oil industry and can be used to reduce the pour point, dynamic viscosity, and also as a means of preventing the formation of asphaltoresin-paraffin deposits (ARPD) during transportation and storage of oil.

Currently, many compounds are described that possess to some extent depressant activity with respect to oil and oil products [1]. Known depressants, as a rule, have a narrow spectrum of action, i.e. copolymers or other classes of chemical compounds with specific properties and structure are used for each type of petroleum product [2]. For example, to improve the low-temperature characteristics of domestic heating fuels boiling in the temperature range 110-500 ° C and solidified at a temperature of -1 to -5 ° C, a copolymer of ethylene and vinyl acetate is introduced, which is previously dissolved in diesel fuel. Depression temperature is 20-25 ° C [3].

Known depressant additives to fuels, which is a synergistic composition of low molecular weight polyethylene or its copolymer with vinyl acetate, containing 15-20% vinyl acetate groups and hydrocarbon solvent containing 20-100% aromatic hydrocarbons. The content of each component in the mixture is from 30 to 70%. Depression of the freezing temperature of the fuel with such an additive is 4 ° C more with its content in the fuel being 0.03 wt. % and 11 ° C at 0.1 wt.%, than with a similar additive without solvent [4].

Known depressant additive representing a copolymer of ethylene with vinyl acetate, modified diphenylamine. With its introduction into the oil, solidifying at + 8 ° С, or in fuel oil, solidifying at + 15 ° С, depression reaches 37 and 35 ° С, respectively. A mixture of aromatic hydrocarbons with diesel fuel is also used as a solvent additive. However, the effect of the additive is limited to the above petroleum products in the patent [5].

A disadvantage of the known depressants is also their limited use, since for each type of petroleum products use their own copolymers, differing in qualitative composition, or with the same composition, different alternation of monomer units and their quantity differ.

Known depressant additive to oils and petroleum products, including a copolymer of ethylene with vinyl acetate, the product of the interaction of 1 mole of higher fatty alcohols fraction C ₁₀ -C ₁₈ with 8-20 moles of ethylene oxide and a hydrocarbon solvent [6]. Known additive is effective when used only for highly paraffin high-melting commercial oils and not technological in application.

There is a method of transporting through the pipeline viscous oils and petroleum products with a high content of asphalt-resin substances, including the introduction into the oil stream in a solvent in a 1: 1 ratio of a mixture of glycopolymer block copolymer and polyalkylbenzene resin, taken in a ratio of 1: 1-4 [7]. The disadvantage of this method is the lack of effectiveness of the reagent used in the transportation of paraffin-resin and low-watered oils and the difficulty of introducing the reagent, which consists in introducing it into the oil stream in a solvent at a certain ratio.

Closest to the claimed additive to the technical essence and the achieved effect is an additive, [8], including a copolymer of ethylene with a polar monomer, a non-ionic surfactant (NSA) and an aromatic solvent, the additive further comprises a ternary copolymer of vinylpyrrolidone, alkyl acrylate and methacrylic acid and / or a copolymer of isobutylene with isoprene, in the following ratio, wt.%:

Ethylene copolymer with polar monomer Triple copolymer of vinylpyrrolidone, alkyl acrylate and methacrylic acid and / or isobutylene copolymer with isoprene non-ionic surfactant Aromatic solvent

2.0-30.0

5.0-10.0

1.0-10.0

rest

In the prototype, the preparation of the composition is carried out by heating at 60-80 ° C, which is a disadvantage of the claimed additive. In addition, before the introduction of the additive into the oil at least 30 ° C, heating is also a disadvantage of this additive.

The objective of the invention is to create a new effective depressant to reduce the pour point and viscosity properties of high-paraffin oils during production, transport and storage of oil, as well as the expansion of the resource base and the range of depressors based on products of various hydrocarbons.

The task in the invention is solved by the fact that the depressant additive consisting of a nonionic surfactant-Laprol 5003-2B-10 or Laprol 6003-2B-18 and a solvent, additionally contains reagent P1exoy SSh 288 and additionally as a nonionic surfactant Laprol 3603-2-12, and as a solvent a stable gas condensate and light gas oil in the following ratio, wt.%:

- 1 029225

20-25

rest

Reagent ΡΙβχοιΊ CM 288

Light gas oil

Laprol 3603-2-12 or Laprol 5003-2V-10 or Laprol 6003-2B-18 Stable gas condensate

15-25

2-5

For the preparation of a depressant as a component with depressant properties, Plyocol PSP 288 reagent, produced by SATrupp TesBpo1odlez, is used. The solvent used is a hydrocarbon solvent-stable gas condensate (TU 51-0575174509-97), and light gas oil (TU 0272-014-79198169-2011). Laprol 3603-2-12, Laprol 5003-2B-10 and Laprol 6003-2B-18 are block copolymers of glycerol-based ethylene and propylene oxides with molecular weights of 3600, 5000 and 6000, respectively. Laprol 3603-2-12 is made according to the technical specification of TSh A3 05757529-77-2003. Laprol 5003-2B-10 and Laprol 6003-2B-18 are manufactured according to TU 2226-02310488057-95 and TU 2226-020-10488057-94.

The introduction of high molecular weight non-ionic surfactant into the composition reduces the surface tension at the ARPA-solvent interface, which increases the efficiency of dissolving and destroying ARPD, and the presence of solvating components in the solvent leads to the solvation of dispersed particles of asphaltenes and paraffins, preventing them from sticking together.

The analysis of the known solutions selected in the search process showed that there is no object in science and technology that is identical with the claimed combination of features and the presence of the above properties and advantages, which allows to conclude that the invention complies with the criteria of "novelty" and "inventive step".

The inventive additive is prepared by simple mixing of the components with stirring. For the preparation of a depressant in a light gas oil, the reagent Plyocol 288 is fed and stirred with a mechanical stirrer for 2 hours at room temperature. After the mixture is homogeneous, laprol 3603-2-12 or laprol 5003-2B-10 or laprol 6003-2B-18 and a hydrocarbon solvent are fed with continued mixing. Mixing the mixture continues until a homogeneous mass is formed for 1 hour. The results of preparing the compositions are given in table. one.

Physico-chemical characteristics of the prepared compositions are as follows: density (at 20 ° C) 8395-8410 kg / m ³ ; kinematic viscosity (at 20 ° С) mm ² / С; dynamic viscosity (at 20 ° С) 19-23 mPa-s; pour point - (20-25 ° C).

To prove the compliance of the claimed invention to the criterion "industrial applicability" provides examples of specific performance.

The depressor properties of the prepared additives are determined for oils taken from production wells No. 202, 453, 456 and 698 of the NGDU named after N.Narimanov of the PA Azneft. Indicators of these oils are given in table. 2

The depressor activity of the proposed additive in various types of oil was tested by reducing the dynamic viscosity (η) (viscometer "81a Vypdeg Vitseur 8UM 300") and pour point (GOST 20287-74). Depressor effect (AT) is calculated by the formula AT = (T _{stagnation. Ref} -T _Saver .pr _uc) [8], where T _{stagnation. the} source temperature of the hardening of the original oil, ° C; T is the temperature _Saver .pr _uc pour oil additive, ° C. The concentration of the additive is 0.02 wt.% Oil.

The results of studies on the depressor effect of additives are given in table. 3

Data analysis table. 2 and 3 suggests that the claimed additive has a high efficiency.

Prepared additives reduce the pour point of oil, which was selected from the production well No. 202, to - (8-18) ° C (AT = 17-26 ° C). In this case, the dynamic viscosity decreases to 65.5-75.4 mPa-s.

- 2 029225

Table 1

No composition Χθχο'ιΙ С \ Л / -288 Non-ionic surfactant Light gas oil Hydrocarbon solvent Laprol 3603-2-12 Laprol 5003-2B-10 Laprol 6003-2B-18 one 2 3 four five 6 7 one 20 2 - - 15 63.0 2 25 2 - - 15 58.0 3 20 3.5 - - 15 61.5 four 25 3.5 - - 15 56.5 five 20 five - - 15 60.0 6 25 five - - 15 55.0 7 20 2 - - 25 53.0 eight 25 2 - - 25 48.0 9 20 3.5 - - 25 51.5 ten 25 3.5 - - 25 46.5 eleven 20 five - - 25 50.0 12 25 five - - 25 45.0 13 20 - 2 - 15 63.0 14 25 - 2 - 15 58.0 15 20 - 3.5 - 15 61.5 sixteen 25 - 3.5 - 15 56.5 17 20 - five - 15 60.0 18 25 - five - 15 55.0 nineteen 20 - 2 - 25 53.0 20 25 - 2 - 25 48.0 21 20 - 3.5 - 25 51.5 22 25 - 3.5 - 25 46.5 23 20 - five - 25 50.0 24 25 - five - 25 45.0 25 20 - - 2 15 63 26 25 - - 2 15 58.0 27 20 - - 3.5 15 61.5 28 25 - - 3.5 15 56.5 29 20 - - five 15 60.0 thirty 25 - - five 15 55.0

31

20

25

53.0

32

33

34

35

25

20

25

20

25

48.0

3.5

3.5

25

25

25

51.5

46.5

50.0

25

25

36

45.0

table 2

No wells Oil density, kc / t ³ Dynamic viscosity oil, mPa-s Temperature Freezing oil, ° C Mass fraction,% paraffins silica gel tar asphaltenes 202 876 149.0 +8 6.0 10.0 0.59 453 899 164.14 +16 19.8 5.4 2.65 456 870 - +18 20.1 15.7 1.53 698 869 168.09 +19 6.9 9.0 0.26

The pour point of oil taken from production well No. 453 decreases to - (6-23) ° С (АТ = 22-39 ° С). Dynamic viscosity decreases to 45.9-48.6 mPa-s.

The pour point of oil taken from production well No. 456 decreases to - (1-13) ° С (АТ = 19-31 ° С). Dynamic viscosity is reduced to 60.9-85.9 mPa-s.

The pour point of oil taken from production well No. 698 decreases to - (2-20) ° С (АТ = 21-39 ° С). The dynamic viscosity decreases to 47.6-51.8 mPa-s.

Due to the possibility of storage and transportation as paraffin, as well as paraffin

- 3 029225

The scope of application of the additive is extended.

Table 3

No composition Well 202 Well 453 Well 456 Well 698 Thaws, n rice, ° s ΔΤ, ° С P. mPas Tast.pris ° s . ^ΔΤ '° C P. mPas Tast.pris ° s ΔΤ, ° С P, mPas Tast.pris ° s ΔΤ, ° С P. mPas one 2 3 four five 6 7 eight 9 ten eleven 12 13 one -eight sixteen 75.3 -6 22 48.3 -one nineteen 85,8 -2 21 49.9 2 -9 17 74.8 -6 22 48.5 -one nineteen 85,6 -2 21 50.1 3 -17 25 67.0 -22 38 46,8 -12 thirty 61.9 -nineteen 38 48.8 four -17 25 65,8 -22 38 47.0 -12 thirty 62.1 -nineteen 38 48.6 five -sixteen 24 68,6 -13 29 47.5 -ten 28 63.5 -sixteen 35 51.7 6 -17 25 67.2 -14 thirty 47.1 -ten 28 63.7 -sixteen 35 51.9 7 -eight sixteen 75.5 -6 22 48.6 -one nineteen 85.9 -2 21 49,8 eight -eight 17 75.4 -6 22 48.3 -2 20 84,8 -2.5 21.5 49.3 9 -17 25 67.1 -21,5 37.5 47.2 -12 thirty 62.0 -nineteen 38 48.7 ten -18 26 65.6 -22 38 46.7 -13 31 61.1 -19,5 38.5 48.1 eleven -17 25 67.0 -13 29 47.3 -ten 28 63.4 -sixteen 35 51.8 12 -17 25 67.2 -13 29 47.5 -10,5 28.5 62.7 -16,5 35.5 51.2 13 -eight sixteen 75.4 -6 22 48.2 -one nineteen 85.9 -2 21 49,8 14 -eight sixteen 75.2 -6 22 48.5 -one nineteen 85.7 -2 21 49,6 15 -sixteen 24 68.7 -21,5 37.5 47.8 -12 thirty 62.1 -nineteen 38 48.6 sixteen -17 25 67.4 -22 38 47.1 -12 thirty 61.9 -nineteen 38 48.9 17 -17 25 67.2 -13 29 47.4 -ten 28 63.4 -sixteen 35 51.8 18 -17 25 67.5 -13 29 47.6 -ten 28 63.6 -sixteen 35 51.6 nineteen -eight sixteen 75.5 -6 22 48.2 -one nineteen 85.7 -2 21 49,8 20 -eight sixteen 75.3 -6,5 22.5 47.3 -1.5 19.5 84,8 -3 22 49.0 21 -17 25 67.1 -22 38 47.1 -12 thirty 61.9 -nineteen 38 48.7 22 -18 26 65.5 -23 39 46.3 -13 31 60.9 -20 39 47.6 one 2 3 four five 6 7 eight 9 ten eleven 12 13 23 -16,5 24.5 67.9 -13 29 46,8 -ten 28 63.5 -sixteen 35 51.8 24 -17 25 67.2 -13,5 29.5 46.0 -eleven 29 62,6 -17 36 50.8 25 -eight sixteen 75.4 -6 22 48.5 -one nineteen 85.7 -2 21 49.9 26 -eight sixteen 75.2 -6 22 48.3 -one nineteen 85.4 -2 21 49,6 27 -17 25 67.4 -22 38 47.5 -12 thirty 62.0 -nineteen 38 48.7 28 -18 26 66.7 -22 38 47.3 -12 thirty 62.3 -nineteen 38 48.9 29 -16,5 24.5 68.0 -13 29 46.6 -ten 28 63.3 -sixteen 35 51.8 thirty -17 25 67.3 -13 29 46.9 -ten 28 63.6 -sixteen 35 51.5 31 -eight sixteen 75.4 -6 22 48.2 -one nineteen 85.7 -2 21 49.9 32 -eight sixteen 75.1 -6,5 22.5 48.4 -2 20 84.6 -3 22 48.8 33 -17 25 67.2 -22 38 46.7 -12 thirty 62.1 -nineteen 38 48.9 34 -18 26 66.7 -23 39 46.0 -13 31 61.0 -20 39 47.8 35 -16,5 24.5 67.9 -13 29 46,8 -ten 28 63.6 -sixteen 35 51.8 36 -17 25 67.2 -14 thirty 45.9 -eleven 29 62.4 -17 36 50.8

Literature

1) Sablina Z.A., Gureev A.A. Additives to motor fuels. M .: Chemistry, 1977, p. 221

2) Sokolov V.G., de Vecchi A.V. The current state and prospects for the development of the synthesis and use of depressant additives to fuels. Oil refining and petrochemistry. 1996, No. 5, p. 27-31

3) Patent CI 2009172, C10B 1/18, 1994.

4) Application for invention CI 93013045/04, C10B 1/14, Bi No. 3, 1996.

5) Patent KI 2024591, S10B 1/18, 1994.

6) Patent CI 2098459, S10B 1/18, 1997.

7) Patent CI 2202730, Ε17Ό 1/17, 2003.

8) Patent Ki 2412233, S10B 1/18. S10B 1/10, 2011.

Claims (1)

CLAIM A depressant additive consisting of a non-ionic surfactant — Laprol 5003-2B-10 or Laprol 6003-2B-18 and a solvent, characterized in that it additionally contains the reagent PF 288 and Laprol 3603-2 -12, and as a solvent - a stable gas condensate and light gas oil in the following ratio, wt.%: The reagent EilehoP school 288 - 20-25. Light gas oil - 15-25. Laprol 3603-2-12, or Laprol 5003-2B-10, or Laprol 6003-2B-18 - 2-5. Stable gas condensate - the rest.